Production of polyazo coloring matters



Patented Nov. 17, 1931 UNITED WALTER M; RALPI I;on nmnunq nnw"103K, assronon "TonAn0m ANIIiiNEQ k CHEMICAL oonrmngrnc; 0F nnw yonx, N11, '1! con ronnnomoninnwfionx J'PRQDUTGTIOhl or ronyezorcononmo' vrnzn rnns 'No Drawing. Application filed ianuary' illls invention relates to the manufacture and production of new polyazocolo-ring mattors, moreparticularly].trisazo coloring matters of the benzidine series.*It -iiicludesthe new productsand theunaterial dyed by the in which: R' we presents can .:a1o1natic radical containingtwo amino groups as :substituents in :lllOLZL-POSllllOllfllO' each othexQP. {ti-CllPhBIlYl radical, or homologue thereof, andf R'pz-anzaroinatic radical, e. g. phenyl, etc. JT-hese'dyestul'ls i are manufactured coupling a tetrazot-ized benzidine body, 6;. g. benzicline,:toli- .dine -.or dianisidine, with 1 one lmolecularpro portion of H's-acid (i..e. 1 S-aminonaphthol- 3 (S-disulfonic acid) in acid solution to-produce a diazo-monazo body (first intermediate) then coupling' this )diazormonazo body in alkaline solution with one molecular: pro- )ortionof a diazo compound (e. g-..o aniline) to produce a diazo-disazo lQQdYEQSGCQllddIltermediate) 3 and finally coupling the. diazodisazo body with one lmoleculargproportion of-auraromatic meta diamine to produce the fiualdyestufi'. l

It is wellknownthat the product-ion of these dyestulfs according tofthe lprocedure outlined above is attended Withfdifliculties, particularly in carrying out the second step wherein the diazo-compoundis coupled with the diazormonazo body (first intermediate) [or the production-of the diazo d-isazofbody or second intermediate. 2 n o "If; in carrying'outthesecondstep for the production of the second intermediate, the

" alkali-is added tothe'diazo=monazobody prior *to the addition otth'e' 'diazo-compoundas the patent directs, then coupling of-one molecule of (li'azounonazo :body with a 56C011l1fi0lecule ot the same lmme diat'elly begins to'tak'e place; an d althoughf the product from 1 such 3;"1927; SerialfiNoxflfiStiDl a coupling is still capable of coupling and of being coupled, nevertheless the product or ;-products resulting from such couplings are both in shade and dyeing properties quite unlike those resulting from coupling one molecule of the diazo compound into one :m'olecule;ofrdiazoemonazolhody..zzllhexamoimt .of conplingzof onermoleculesot diazoimonazo body- -with:another molecule 10f thezsaixheadependsnn ainlymponzthelazpsezofztimesbetween M0 the :additioinofithemlkalisandtthewsuhsequent addition lofuthez diazo zcompound. ,3 Eor. this vneason: currentspraotice"idiffcrsi rfzrbmuthe :i'directions of the patent in thatnthesafiidjdiazo compound is added tot-the acid suspension of {'5 the diazo-monazo body and the mixture then made alkaline. Understhesemconditions, and particularly Wheng a distinct excess of the diazo compoundis -enrployed, amuch more homogeneous product is obtainedrthanwhen L70 the directionsofthe patent'arefollowed, and the yield 'offini'sh'ed 'dyestillf is" markedly improved. i

"The excess of-the" diazocomp'ound remaining atthe completion bfthefsecoiidcqupling.

is an undesirable 'featureQofthe reaction since, unless \destroyedior otherwise removed ,prior tothe final coupling with" the metadiamine, it couples with said 7 Ineta diainine produces a chrysoidine' or chry'soidine-hke body.

tion by allowing the mix-turezto stand, by the 1195' aid of heat or bythe aid of chemical agents 1-ivhich:-:decomposefit:and;fiomnrzthereffiomiend iproducts which.eareimottdyestufis grror moupfingrvith' variouszisimplessubstaneesstostorm --dyestuflsfwhitch atrefieitherfleliminatedrin rth'e mother liquor from the final filtration of the finished product or left in the final dyestuff, if their presence in the final dyestuif is not mediate as Well,thus entailing a large. loss in, 7 yield of the final dyestuffand contaminating" itwith objectionable impurities.

According to the present invention, I have found that, when monazo dyes capable of being coupled with diazo compounds are added;

to the alkaline mixture containing the un combined excess of diazo compound and the diazo-disazo body (second intermediate),

very little or no coupling takes place between the diazo-disazo body and the monazo dyestuff whereas the diazo compound couples easily and quickly with the monazo dyestufi'.

- The use of monazo dyes having the following probable formula 5 Y run on H0PN=N rio=s S0311 in which P represents a diphenyl radical or a derivative thereof, have been found to be particularly advantageous since they readily couple with the. diazo compound to give products or a product-which is identical with or closelyrelated to products normally occurring in small quantitiesin the final trisazo dyestufi as a result of the unavoidable thermald'ecompositionof diazo groups during the various steps of manufacture. Their resencein the final trisazo dyestuff is unob- JectiOnable and'adds to the tinctorial value of the whole.

.These particular monazo dyes arepreferably prepared by the hydrolytic decomposition of the diazo-monazo dye which is obtained as the first intermediate in the process for making the final trisazo dye. They'readily combine with'diazo compounds to give dyestuffs having the following probable formulazf Y Hm I on whereP represents a diphenyl nucleus which -may 'containsubstituents and R a radical'of the aromatic series, for example, phenyl, etc. Due to the removal of the excess diazo compound in the aforesaid manner the final trisazo dyestuff prepared from a diazo-disazo product so processed is substantially free from chrysoidine bodies.

The following specific example will further illustrate the invention, it being understood that' the invention is not limited thereto. I

EwamplerrToa well-stirred alkaline solution at a temperature of about 0-2 C., which contains diazobenzene sulfate in relatively small amount and a. suspension of the diazodlsazo. intermediate body which in the free state probably corresponds with the following formula SOsH HaN OH and which has been produced in any well known manner, for example, by first coup- 1mg 1 8-aminonapthol-3: 6-disulfonic acid (one mole) in acid solution with tetrazotized benzidine (one mole) and then with diazobenzene in alkaline solution (a slight excess of one mole of diazo-benzene sulfate being employed-incarrying out the second coupling), there isslowly added a cold, dilute (two to three percent) alkaline solution of pphydroxydiphenyl 7 azo 3 6 disulfo 8- amino-l-napthol (prepared in any suitable manner, for example, by-boiling pp'-diazodipl1enyl-'Z-aZo-3 6-disulfo-8-aminol -napl1 thol in-dilute sulphuric acid and subsequently dissolving the product thus obtained, without isolation, in caustic soda or sodium carbonate) until a sample of the reaction mixture when tested by treating it with common salt and then with a suitable coupling reagent shows the absence of diazobenzene. The resulting solution containing the diazo-disazo body in suspension and now free from the.

presence of any diazo-benzene is then coupled with one molecular proportion of mphenylenediamine, 'or m-tolylenediamine or other suitable aryldiamine in any well known or suitable manner, and the dyestuff isolated in the usual way, e. g., by salting out.

In the above example, the free diazobenzene which is present readily. combines with the pp hydroxydiphenyl 7 -azo- 3 6 disulfo 8 amino-'l-napthol and produces a dark to bluish-green disazo dyestuif while the diazodisazo body reacts very'little, if at all, with it. Since the solution is free, orsubstantially so, from the presence of diazobenzene, the trisazo dyestuff. thus finally produced by coupling the diazo-disazo body with mphenylenediamine, .orwith nl-tolyenediamine or other suitable aryldiamines, is'substantially free fromja chrysoidine body which would be otherwise produced by the action of ICC ' little or not at all.

sulting final dyestuff isa dark powder, soludiazobenzene on:theraryldiamine. Tliewdeirl;

to-bluishagreen disazoadyestufiis' precipitated and isolated in admixtureswith the: trisazo dyestuif but "its: presence 1 is not harmful: and

dyeings oncotton are: readily discharged to ttwWhltG. Further, it stains acetate silk very In the dryrstate, thereble in water and in concentrated sulfuric acid, and dyesunmord'anted cotton Various shades of black which are readily discharged to a white. It issubst'antially free from chrysoidine bodies and stains acetatesilk Very little or not at all. The-final dyestufl produceclwhe'n msphenylenediamine is used in the'final coup'lingjisadark powder soluble in water with 'a greenish-black toblack color, and in concentrated sulfuric acid with a blueblack color whi'chon dilution with water gives a red'dish bla'ck'precipitate; It idy'es unmordanted cotton -greenish to bluish sha'des of black.

In a similar manner, in the production of a trisazo coloring matter by con ning an aryldiamine witha diazo-disazobody wherein the diazo-disazo body isprepared by coupling anexcess of a 'diazo compound-with a .diazo-V of the benzidine series and a portion ofthe diazotized aromatic amino-body is present in the uncombined state in the reaction mixture at the end of the reaction, theimproyement which comprises treating thesaid reaction mixture obtained at the end of the reaction with a mona-zo dyestufi, which is capable of reacting with the said uncombined diazotized aromatic amino-body, whereby said uncombined diazotized aromatic aminobody is converted into a disazo'body.

2..In the production of a trisazo dyestufl, the improvement which comprises treating a reaction mixture containinga diazo-disazo compound of the ben zidine series and a diazo compound, said reaction mixture resulting from rea :ting a cliazo compound with a diazomona'zo compound" of the benzidine-series,

with an 2120 dyestufl' deriyed the hydrol'ytic decomposition of the saiddiazo-monaz'o compound, whereby said diaao compete-a re' gaze ' c 3, In the production of a diazo -disazo int ermediaterproduct obtainable by treating with diazohenzene adi'azo-monazo bodyhavmg the: following formula mi e .on

Na'O3S SOaNa' where represents an acid grOup andEP denotes a diphe-nyl radical, and wherein a residual amount of uncombined diazobenzene is present in th-e" reaction mixture, the improvement which comprises incorporating with the reaction mixture a monazo dye having the followingprobable. formula: 1 a,

, 11m on where P represents diphenyliradical and coupling said 'monazo dye with the residual diazobenzene present.

- at. In the production of 'polya zoacoloring matters by first coupling a tetrazotized benzidine body with acid in acid solution,

then coupling the resulting. dia-zo' monazo intermediate product with anexcess ofa monodiazo-compoundin alkaline solution, and

finally coupling, thediazo-disazo body thus obtained with an 1 aromatic metaediam ne, a

process which comprises, incorporating a solution containing the di azo-disazo body, and residual monodiazo compound witha solu- ,tion of amonazo dyestufiderived from the diazo-monazo intermediate product by hydrolytic; decomposition in an .amount ,sufii- V cient only to combine with the residual monodiazo compound present, and subsequently ;'5."'I-n tlie production ofa tris az o dyestuff, the improvement which comprises treating a reaction "mixture containing a a diazotized aromatic amine of the benzene series and: a

diazo-disazobody ofthe benzidineseries havingthe "following probableuformula:

I a HQNQ'oH' in which X represents anaci'dradi'caI PZaa diphenyl nucleus which maycontain: substituents, and R athydrocarbon radical vo-fithe benzene series, with a monazo dyestufighaving the following probable formula:

in which P stands for the same grouping as P, the amount of said monazo dyestuif em ployed being just suflicient to combine with the said diazotized aromatic amine which is present, to form a disazo dyestufi', and subsequently coupling the diazo-disazo body 7 with an aromatic meta-diamine.

' sponds with the 6; In the production of polyazo coloring matters by coupling an aromatic metadiamine of the benzene series with a diazodisazo body which in the free state correprobable formula:

in which X represents an acid group, and P a diphenyl nucleus which may contain sub-- st1tuents,-a process which comprises treating the solution containing the diazo-disazo body with a solution of a monazo dyestuff which in the free state corresponds with the probable formula:

. HzN

OH I l HOaS son:

in which P represents a diphenyl nucleus which may contain substituents, in amount just sufficient to combine with any diazobenzene which may be present, and subsequently coupling the ,diazo-disazo body, which is free from diazobenzene, with the aromatic metadianiine.

7. In the production of polyazo coloring matters by coupling m-phenylenediamine with a diazo-disazo body which in the free state corresponds with'the probable formula:

' H O as in which X represents an acid group, a process which comprises treating the solutioncontaining the diazo-disazo body with an alka: line solution of-pp-hydroXy-diphenyl-7'-azol 8-amino-naphfthol-3 G-disulfonic acid in amount just sufiicient to combine with any diazobenzene which may be present, and subsequently coupling the diazo-disazo body,

1 which is free from diazobenzene, with the mphenylenediamine..- v 8. As a new product, the polyazo coloring matter free from a chrysoidine body, and 7 comprising a trisazo dyestulf having in the free statethe following probable formula:

I Hay n:

wherein R signifies an aromatic radical containing two amino groups as substitutes, P a diphenyl nucleus which may contain substituents, and vR a radical of the aromatic series, in admixture with a disazo dye having in the free state the following probable formula: 1 v o HaN HOaS in which P represents a'diphenyl nucleus which may contain substituents, and R a radical identical with that similarly designated in the trisazo dyestuff component.

9. As a new product, the-polyazo coloring matter which is free from chrysoidinebodies,

and comprising a trisazo dyestuif of the followingprobable formulai y Y HZN on HOsS SOsH in which P represents a diphenyl nucleus which may contain substituents, and R a hydrocarbon radical identical with that similarly designated in the trisazo dyestuif component. I a

10. As a new product, the polyazo dyestuff which is free from chrysoidine bodies, and which comprises a trisazoidyestufl' of the following probable formula: v 7

wherein Rsignifies a meta-diamine radical ofthe benzene series, P a diphenyl nucleus which may containsubstituents, and R a hydrocarbon radical of the benzene series, in admixture with a disazo dyestufi having the following probable formula HaN OH wherein P represents a diphenylnucleus and R a hydrocarbon radical identical with that present and similarly designated in the trisazo dyestufi component.

11. As a new product, the polyazo dyestuif which is free from chrysoidine bodies, and which comprises a trisazo dyestufl? of the following probable formula:

NH: mu 0H 7 l HO; $0.11

in admixture with the disazo dyestuif having the following probable formula: I

v HIN OH I Hogs soul v 12. Material dyed with the dyestufi' of claim 8.

13. Material dyed with the dyestufl' of claim 9.

14. Material dyed with the dyestufi of claim 10.

15. Material dyed with the dyestufi of claim 11.

In testimony whereof I atfix my signature.

WALTER M. RALPH.

Certificate of Correction Patent No. 1,832,322. Granted November 17, 1931, to WALTER M. RALPH It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 1, line 88, for contamination read contaminating page 2, line 127, for m-tolyenediaread m-tolyl enedia age 4, line 67, claim 8, for substitutes read substtuents; page 5, between lines 15 and 20, claim 11, strike out the formula and insert instead NHz and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 29th day of December, A. D. 1931.

[SEAL] M. J. MOORE,

Acting Omnmissioner of Patents. 

